US5138075A - Extractive separation method - Google Patents

Extractive separation method Download PDF

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US5138075A
US5138075A US07/799,010 US79901090A US5138075A US 5138075 A US5138075 A US 5138075A US 79901090 A US79901090 A US 79901090A US 5138075 A US5138075 A US 5138075A
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solvent
solute
temperature
mixture
critical
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Kazunari Ohgaki
Takashi Katayama
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Kuraray Co Ltd
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Kuraray Co Ltd
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Priority claimed from JP5188484A external-priority patent/JPS60197669A/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B01D11/0403—Solvent extraction of solutions which are liquid with a supercritical fluid
    • B01D11/0407—Solvent extraction of solutions which are liquid with a supercritical fluid the supercritical fluid acting as solvent for the solute
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B1/00—Production of fats or fatty oils from raw materials
    • C11B1/10—Production of fats or fatty oils from raw materials by extracting
    • C11B1/104—Production of fats or fatty oils from raw materials by extracting using super critical gases or vapours
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/006—Refining fats or fatty oils by extraction
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/10—Refining fats or fatty oils by adsorption

Definitions

  • the present invention relates to an extractive separation method for separating an extract (a solute) in the supercritical phase thereof wherein the extraction is carried out by means of a solvent in the sub-critical phase thereof.
  • This technique consists in that organic or inorganic substances, which are gaseous at the atmospheric temperature and an atmospheric pressure, are pressurized at temperatures over the critical temperature thereof to increase the density thereof and the extraction is carried out by utilizing the dissolving power thereof improved owing to an increase in the density thereof.
  • this technique is advantageous in respect of energy since it does not require the separation means, which is accompanied with the changes in phase of substances such as cooling and distillation, for the separation of a solute from a solvent differently from the usual liquid-liquid extraction.
  • these known supercritical-fluid extraction methods consist in the repetition of the operation that a medium is brought into contact with a solvent under a superhigh pressure of for example 5 to 6 times the critical pressure to extract the desired solute contained in the medium and then the solute is separated from the solvent by remarkably reducing the pressure and/or temperature to reduce the dissolving power of the solvent.
  • Such an object can be achieved by a method wherein a medium containing solutes consisting of organic substances is brought into contact with a solvent having the critical temperature of 5° to 152° C. and consisting of organic or inorganic substances, which are gaseous at an atmospheric temperature and pressure, to extract the solutes from the medium and then the solutes are separated from the mixture of extracts, characterized by that said solutes and solvent are selected from the combinations forming the mixture systems having an additional gas-liquid coexistence region, the extraction being carried out by bringing said medium into contact with said solvent in the sub-critical phase of said solvent, and the subsequent separation being carried out with heating said mixture of extracts to temperature higher than the critical temperature of said solvent by 5° to 30° C.
  • FIG. 1 is a binary system phase equilibrium diagram of solute-solvent at the sub-critical temperature of T 1 .
  • FIG. 2 is a phase equilibrium diagram at temperatures of T 2 higher than the critical temperature T c and lower than the temperature T.sub. ⁇ at which an additional gas-liquid coexistence region disappears.
  • FIG. 3 is a phase equilibrium diagram at the temperature T.sub. ⁇ .
  • FIG. 4 is a phase equilibrium diagram at temperatures T 3 still higher than the temperature T.sub. ⁇ .
  • FIG. 5 is an enlarged diagram showing additional gas-liquid coexistence regions shown in FIGS. 1 to 4.
  • FIG. 6 is a diagram showing critical lines for octadecane-CO 2 system.
  • FIG. 7 is a diagram showing critical lines for decane-CO 2 system.
  • FIG. 8 is a flow chart showing an example of an extractive separation method according to the present invention.
  • Said additional gas-liquid coexistence region is a gas-liquid coexistence region at pressures higher than a gas-liquid-liquid three-phase coexistence pressure if the system is binary as indicated by an oblique lined portion in a solute-solvent binary system phase equilibrium diagram at the sub-critical temperature T 1 shown in FIG. 1.
  • 2 designates a liquid-liquid phase
  • 3 designating a liquid phase
  • 4 designating a gas-liquid phase
  • 5 designating a gas phase.
  • 6 designates the gas-liquid-liquid three phase coexistence pressure
  • 7 designates the critical point.
  • FIG. 2 is a solute-solvent binary system phase equilibrium diagram at temperatures T 2 higher than the temperature T c and lower than the temperature T.sub. ⁇
  • FIG. 3 is a solute-solvent binary system phase equilibrium diagram at the temperature T.sub. ⁇ . 8 designates a fluid-fluid phase.
  • Such an additional gas-liquid coexistence region disappears at the temperature T.sub. ⁇ .
  • FIG. 4 is a solute-solvent binary system phase equilibrium diagram at temperatures T 3 still higher than the temperature T.sub. ⁇ .
  • the conventional supercritical-fluid extraction method consists in that the extraction is carried out under the conditions shown in FIG. 4, for example, at superhigh pressures of 5 to 6 times the critical pressure and then the pressure and/or the temperature is remarkably reduced to extract the solutes from the solvent.
  • FIG. 5 is an enlarged diagram showing additional gas-liquid coexistence regions shown in FIGS. 1 to 4.
  • 9 designates an additional gas-liquid coexistence region at the sub-critical temperature T 1
  • 10 designating an additional gas-liquid coexistence region at the temperature T 2
  • 11 designating an enlarged gas-liquid equilibrium diagram at the temperature T.sub. ⁇
  • 12 designating an enlarged gas-liquid equilibrium diagram at the temperature T 3 .
  • A designates a point on an equilibrium curve at the temperature T 1
  • B designates a point on an equilibrium curve at the temperature T.sub. ⁇ .
  • An extractive separation method utilizes the radical change in a phase equilibrium within such an additional gas-liquid coexistence region. This will be easily understood from the explanation that it is necessary only to heat the mixture of extracts having the composition corresponding to the point A on the equilibrium curve at the temperature T 1 in FIG. 5 to the temperature T.sub. ⁇ higher than the temperature T 1 by 5° to 30° C. in order to separate the solutes of an amount excepting that corresponding to the equilibrium composition B at said temperature T.sub. ⁇ .
  • solutes to be extracted and the solvent to be used form the mixture system having an additional gas-liquid coexistence region or not can be judged by knowing where the critical lines of a solute-solvent binary system are discontinuous or not. That is to say, it is found that the critical lines are discontinuous and an additional gas-liquid coexistence region exists between two components of said solutes and said solvent whereby being capable of carrying out an extractive separation method of the present invention if the lines drawn from the solvent side cross a liquid-liquid coexistence plane or a solid-liquid coexistence plane to terminate halfway whereby disagreeing with the lines drawn from the solute side when the critical lines of a solute-solvent binary system are drawn in accordance with a Heidemann's method [AIChE Journal., 26 (5), 769-779 (1980)].
  • the critical lines can be determined by solving the equation of state of a solute-solvent binary system and the limit of stability about the phase diffusion. It is known that the state in mixtures is accurately described by the following Soave-Redlich-Kwong's equation: ##EQU1## wherein P designates pressure, R designating gas constant, T designating temperature, and v designating molar volume. a and b, which are constants proper to each component, are calculated from the following equations: ##EQU2##
  • a ii , a jj and b i for each pure component are determined by the following equations: ##EQU3## wherein Tc designates critical temperature, Pc designating critical pressure, Tr designating reduced temperature, ⁇ designating acentric factor (Pitzer), and i and j designating the i-th and the j-th component, respectively.
  • Tc, Pc and ⁇ are proper to substances and detailedly described in R. C. Reid, J. M. Prausnitz and T. K. Sherwood, "The properties of Gases and Liquids, Appendix A Property Data Bank” (1977) Mc Graw-Hill Book Co. However, when not described in the above described, they can be estimated from the molecular structure in accordance with the method described in A. L. Lydersen, "Estimation of Critical Properties of Organic Compounds" (1955).
  • k ij can be determined if there is a phase equilibrium data at an optional point. Even though there are no phase equilibrium data, it can be estimated from, for example, the values of thermodynamic properties such as the data of heat of mixing since they are expressed by the function of k ij and this function can be easily solved.
  • the fugacity coefficient can be calculated by the following equation (4): ##EQU4## wherein ⁇ i designates fugacity coefficient, V designating volume, and Z designating compressibility factor.
  • equation (5) there is the relation expressed by the following equation (5) between fugacity fi and fugacity coefficient ⁇ i:
  • ⁇ designates chemical potential
  • ⁇ n designating a change in molar number
  • suffix i designating the i-th component
  • 0 designating test point
  • the critical temperature T c and the critical volume V c can be determined by solving the equations (9) to (11).
  • P c can be determined from T c and V c by the equation (1).
  • the critical lines for an octadecane-CO 2 system and those for a decane-CO 2 system drawn by the above described method are shown in FIG. 6 and FIG. 7, respectively.
  • 13 designates the critical lines for an octadecane-CO 2 system
  • 14 designating the critical lines for a decane-CO 2 system
  • 15 designating an end point.
  • C 1 designates the critical point for CO 2
  • C 2 designating the critical point for octadecane
  • C 3 designating the critical point for decane.
  • An octadecane-CO 2 system is one example, to which an extractive separation method according to the present invention can be applied, since the critical lines for an octadecane-CO 2 system are discontinuous and an octadecane-CO 2 system forms a mixture system having an additional gas-liquid coexistence region.
  • a decane-CO 2 system is one example, to which an extractive separation method according to the present invention can not be applied, since the critical lines for a decane-CO 2 system are continuous and a decane-CO 2 system does not form a mixture system having an additional gas-liquid coexistence region.
  • the components of the solute can be extracted and separated by a method of the present invention if the critical lines for every combination of the component of the solute and the component of the solvent are discontinuous.
  • Other components of the solute also can be extracted and separated if the critical lines for them are discontinuous. It can be found by drawing the critical lines in such a manner that a plurality of solutes can be simultaneously extracted or a single solute can be selectively extracted.
  • the medium contains two or kinds of solute forming the above described additional gas-liquid coexistence region when contacted with the solvent
  • the mixture of solutes can be separated into components thereof by applying again a method of the present invention with using other solvents forming a mixture system having an additional gas-liquid coexistence region merely for the specified solute or using the usual means such as distillation.
  • Every organic substance forming an additional gas-liquid coexistence region with a solvent can be selected as a solute which can be extracted and separated by a method of the present invention. It includes hydrocarbons such as octadecane, decane, eicosane, naphthalene, decalin, tetralin, pinene, pine oil and biphenyl; hydrocarbon halogenides such as 2-ethyl hexyl chloride, dichlorobenzene, trichlorobenzene, bromobenzene, dibromobenzene and chlorotoluene; alcohols such as n-hexanol, n-octanol, 2-ethyl hexanol, nonanol, n-decanol, undecanol, n-dodecanol, benzyl alcohol, ethylene glycol, propylene glycol and glycerine; ethers such as n-hexyl
  • every liquid or solid organic or inorganic substance which is insoluble to a solvent or does not form a mixture system having an additional gas-liquid coexistence region with the solvent used under the extracting conditions, can be used as a medium containing solutes therein. It includes various kinds of hydrocarbon, alcohols, polystyrene, copolymers of polystyrene and divinylbenzene, polymeric adsorbents such as active carbon and alumina and inorganic adsorbents.
  • a medium containing solutes therein includes vegetables and wild grasses such as mugwort, dill, parsley, celery, fennel, pepper and ginger; seeds and cereals such as cacao, vanilla, nuts, cotton and juniper; foodstuffs such as hop, yeast, milk and yolk of an egg; tocopherol-containing vegetable fats and oils; and the like. Every fat and oil extracted from vegetable seeds, fruits, leaves, roots and the like containing tocopherol can be used as said tocopherol-containing vegetable fats and oils.
  • It includes palm oil, coconut oil, cotton-seed oil, germ oil, linseed oil, peanut oil, rape seed oil, rice-bran oil, sesame oil, soy bean oil, safflower oil, carrot oil, corn oil or the mixtures thereof.
  • the solvent used in the present invention is an organic or inorganic substance with the critical temperature of 5° to 152° C., preferably 15° to 120° C. It is suitably selected from the group consisting of carbon dioxide (CO 2 ), carbon subsulfide, hydrogen bromide, hydrogen chloride, hydrogen sulfide, nitrous oxide, phosphine, radon, ethane, propane, propylene, acetylene, freon and the like or the mixtures thereof with taking the combination with a solute to be extracted thereof into consideration. It is undesirable to use organic or inorganic substances, which have the critical temperature lower than 5° C. or higher than 152° C. and are gaseous at an atmospheric temperature, for the solvent since the operating temperature is severe.
  • a method of the present invention can be in particular advantageously applied to the extraction and separation of tocopherol from tocopherol-containing vegetable fats and oils by the use of the solvent substantially consisting of carbon dioxide.
  • tocopherol can be obtained under gentle operating conditions with a lower energy consumption, high efficiency and high selectivity.
  • the residual vegetable fats and oils after the separation of tocopherol for example, palm-nut oil can be used as various kinds of industrial material.
  • crude vegetable fats and oils contain components having uncomfortable odor. Accordingly, it is inevitable to refine them by the deodorizing process.
  • odorless fats and oils can be obtained.
  • the residual fats and oils without requiring the additional deodorizing process can be obtained.
  • a solvent, which substantially consists of carbon dioxide, in the present invention is generally one consisting of carbon dioxide only. It includes, however, also carbon dioxide, to which organic or inorganic substances having the critical temperature of 5° to 152° C. and being gaseous at an atmospheric temperature and an atmospheric pressure are added, so far as the characteristic of forming a mixture system having an additional gas-liquid coexistence region for tocopherol is essentially held.
  • the extraction is carried out by bringing a medium containing solutes into contact with a solvent in the subcritical phase of said solvent and the subsequent separation is carried out by heating the mixture of extracts to temperatures of the critical temperature of said solvent or more and higher than the contact temperature by 5° to 30° C., preferably 7° to 20° C.
  • the contact temperature is lower than the critical temperature of the solvent, an advantageousness in respect of energy is reduced when the difference between temperatures in the extracting process and those in the separating process is too large while an extracting efficiency is reduced when the difference between temperatures in the extracting process and those in the separating process is too small.
  • the extracting temperature is lower than the critical temperature of the solvent by 5° to 20° C., preferably 5° to 10° C.
  • the pressure used in the present invention must be selected so that the solubility of the solute to the solvent at the extracting temperature determined in dependence upon the kind of the solvent used may be larger than the solubility of the solute to the solvent at the separating temperature determined in dependence upon the kind of the solvent used alike to said extracting temperature, it is preferable to select the pressure so that the difference between said solubilities may be maximum. Accordingly, it is suitable to select the solvent from the group consisting of substances by means of which the extraction and separation can be carried out at lower temperatures and pressures.
  • tocopherol is extracted with carbon dioxide as a solvent from tocopherol-containing vegetable fats and oils in the present invention
  • carbon dioxide as a solvent from tocopherol-containing vegetable fats and oils
  • the extracts mainly comprising tocopherol containing triglycerides are separated from the solvent containing a remarkably large amount of free acid. Since it is undesirable to recycle the solvent containing free acids for the extraction, said solvent is held at pressures lower than the pressure, at which tocopherol is separated from the solvent, by 0.1 to 5 MPa, preferably 1 to 4 MPa, to separate free acids therefrom whereby recovering the solvent in the form suitable to the recirculation.
  • the initial feed of carbon dioxide as a solvent into said extractor 16 is carried out by means of a pump 28.
  • a pump 28 Although every vessel, which is pressure resistant and corrosion resistant, can be used as said extractor 16, an autoclave and a packed tank are usually used.
  • the temperature of a heater 19 and a cooler 29 is set to the appointed one.
  • Tocopherol-containing vegetable fats and oils and the solvent are circulated in the system by operating a compressor 27.
  • the pressure of said extractor 16 is adjusted by a pressure-regulating valve 18.
  • the mixture of extracts passes through a piping 17 and is heated in said heater 19.
  • the heated mixture consisting of carbon dioxide, tocopherol and free acids is introduced into the first separator 20.
  • Said first separator 20 is held under the same pressure as said extractor 16 by means of a valve 22.
  • Said mixture is separated into the fraction comprising tocopherol as the main component and carbon dioxide containing free acids.
  • a separator of every type, in which tocopherol can be separated from said mixture of extracts, can be used as said first separator 20.
  • the usual mist separator, packed tank and the like are used.
  • the extracts containing tocopherol as the main component are discharged through an extracting valve 21 and the mixture consisting of free acids, which hardly contain tocopherol, and carbon dioxide is introduced into the second separator 23.
  • a separator of every type can be as said second separator 23, ones of the same type as said first separator 22 are usually used.
  • Said second separator 23 is operated under the pressure lower than that of said first separator 22 by 0.1 to 5 MPa.
  • Free acids are separated from carbon dioxide in said second separator 23.
  • the pressure in the system is regulated by a pressure-regulating valve 25. Free acids are discharged out of the system through an extracting valve 24.
  • Carbon dioxide passes through a piping 26, being compressed again by means of a compressor, being regulated in temperature in said cooler, and then being fed again into said extractor 16. Carbon dioxide lost in the operation is supplemented by means of said pump 28.
  • the mixture of tocopherol and triglycerides obtained in said first separator 20 can be separated into tocopherol and triglycerides by the usual separating means such as distillation.
  • an extractive separation method of the present invention is positioned between the conventional supercritical-fluid extraction and an extraction with liquefied high-pressure gases, according to a method of the present invention, an extractive separation can be carried out under the gentler operating conditions than those in the conventional supercritical-fluid extraction and an extraction with liquefied high-pressure gases. Accordingly, a method of the present invention is an extractive separation method effective in cases where a solvent is circulatingly used. A method of the present invention is particularly effective in cases, where a medium is tocopherol-containing vegetable fats and oils and carbon dioxide is used as a solvent, since not only tocopherol can be efficiently and very selectively extracted and separated but also odorless fats and oils can be obtained.
  • An octadecane (solute)-CO 2 (solvent) system shows discontinuous critical lines as shown in FIG. 6, said two components forming a mixture system having an additional gas-liquid coexistence region.
  • CO 2 can dissolve a maximum amount of octadecane therein at 25° C. and 8.0 to 10 MPa.
  • An oleic acid (solute)-CO 2 (solvent) system shows discontinuous critical lines similarly to the solute-solvent system of EXAMPLE 1.
  • CO 2 can dissolve a maximum amount of oleic acid therein at 25° C. and 8.0 to 10 MPa.
  • a decane (solute)-CO 2 (solvent) system shows continuous critical lines as shown in FIG. 7, said two components not forming a mixture system having an additional gas-liquid coexistence region.
  • 50% by weight-solution of decane in triglyceride of 40 g fed into an autoclave as used in EXAMPLES 1, 2 were treated for 8 hours under the same conditions as in EXAMPLE 1 but decane could not be obtained at all.
  • Palm-nut oil which contained ⁇ -tocopherol at a ratio of 0.10% by weight and free acids at a ratio of 0.06% by weight, of 100 g fed into an autoclave having an internal volume of 150 ml was subjected to the extraction with carbon dioxide at the sub-critical temperature of 25° C. CO 2 was fed into said autoclave held at a pressure of 10 MPa and a temperature of 25° C. at a rate of 0.6 g/min to extract ⁇ -tocopherol. Then said mixture of extracts was heated to 40° C. in a heater with holding the pressure constant and it was separated into a component containing ⁇ -tocopherol as the main ingredient and carbon dioxide containing free acids in the first separator.
  • Carbon dioxide containing free acids was separated into free acids and carbon dioxide in the second separator held at a pressure of 6.0 MPa and a temperature of 25° C. Carbon dioxide was regulated in temperature again to circulatingly use. After operating about 1.5 hours under these conditions, a mixture of 126.4 mg consisting of ⁇ -tocopherol of 84.7 mg and triglyceride of 41.7 mg was obtained from the first separator and a mixture of 63.2 mg containing free acids of 57.5 mg was obtained from the second separator.
  • tocopherol can be very selectively extracted and separated according to the present invention.
  • crude palm-nut oil showed an offensive odor, it did not show an offensive odor after treating by a method of the present invention.
  • coconut oil which contained ⁇ -tocopherol at a ratio of 0.11% by weight and free acids at a ratio of 0.07% by weight, of 100 g fed into an autoclave having an internal volume of 150 ml was subjected to the extraction with carbon dioxide at the subcritical temperature of 30° C. Carbon dioxide was fed into said autoclave held at a pressure of 10 MPa and a temperature of 30° C. at a rate of 0.6 g/min to extract ⁇ -tocopherol. Then said mixture of extracts was heated to 40° C. in a heater with holding the temperature constant to separate into a component containing ⁇ -tocopherol as the main ingredient and carbon dioxide containing free acids in the first separator.
  • Carbon dioxide containing free acids was separated into free acids and carbon dioxide in the second separator held at a pressure of 7.0 MPa and a temperature of 30° C. Carbon dioxide was regulated in temperature again to circulatingly use. After operating about 1.5 hours under these conditions, a mixture of 124.9 mg consisting of ⁇ -tocopherol of 83.6 mg and triglyceride of 41.3 mg was obtained from the first separator and a mixture of 62.5 mg containing free acids of 56.3 mg was obtained from the second separator.
  • tocopherol can be very selectively extracted and separated according to the present invention.
  • crude coconut oil showed an offensive odor, it did not show an offensive odor after treating by a method of the present invention.
  • Palm-nut oil which contained ⁇ -tocopherol at a ratio of 0.10% by weight and free acids at a ratio of 0.06% by weight, of 100 g fed into an autoclave having an internal volume of 150 ml was subjected to the extraction with carbon dioxide at 40° C. Carbon dioxide was fed into said autoclave held at a pressure of 15 MPa and a temperature of 40° C. at a rate of 0.6 g/min to extract ⁇ -tocopherol. Then the pressure of said mixture of extracts was reduced to 10 MPa with holding the temperature constant to separate said mixture of extracts into a component containing ⁇ -tocopherol as the main ingredient and carbon dioxide containing free acids in the first separator.
  • Carbon dioxide containing free acids was separated into free acids and carbon dioxide in the second separator held at a temperature pressure of 9.7 MPa and a temperature of 39° C. Carbon dioxide was regulated in temperature again to circulatingly use. After operating about 2.0 hours under these conditions, ⁇ -tocopherol of merely 45 mg was obtained from the first separator. In addition, the separation of free acids in the second separator was incomplete, so unseparated free acids were circulated in the system and the selectivity for ⁇ -tocopherol was remarkably low as indicated by a ratio of ⁇ -tocopherol to triglyceride by weight of 54:46.
  • Palm-nut oil which contained ⁇ -tocopherol at a ratio of 0.10% by weight and free acids at a ratio of 0.06% by weight, of 100 g fed into an autoclave having an internal volume of 150 ml was subjected to the extraction with carbon dioxide at 80° C. Carbon dioxide was fed into said autoclave held at a pressure of 35 MPa and a temperature of 80° C. at a rate of 0.6 g/min to extract ⁇ -tocopherol. Then the pressure of said mixture of extracts was reduced to 30 MPa with holding the temperature constant to separate said mixture of extracts into the solute and the solvent. After operating about 1.5 hours under these conditions, extracts of 659 mg were obtained. But the composition of said extracts was almost same as the composition of crude palm-nut oil. That is to say, ⁇ -tocopherol could not be selectively obtained.

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JP58-122549 1983-07-05
JP12254983A JPS6014901A (ja) 1983-07-05 1983-07-05 抽出分離方法
JP59-51884 1984-03-16
JP5188484A JPS60197669A (ja) 1984-03-16 1984-03-16 トコフエロ−ルの抽出分離方法

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US5445841A (en) * 1992-06-19 1995-08-29 Food Sciences, Inc. Method for the extraction of oils from grain materials and grain-based food products
US5591772A (en) * 1991-11-22 1997-01-07 Lipogenics, Inc. Tocotrienols and tocotrienol-like compounds and methods for their use
US5620728A (en) * 1993-02-01 1997-04-15 Food Sciences, Inc. Method and apparatus for the extraction of oils from grain materials and grain-based food products
US5626756A (en) * 1994-12-29 1997-05-06 Skw Trostberg Aktiengesellschaft Process for fractionating and refining natural lipid substances
US5653884A (en) * 1994-07-09 1997-08-05 British Nuclear Fuels Plc Separating solutes from solutions
US5756657A (en) * 1996-06-26 1998-05-26 University Of Massachusetts Lowell Method of cleaning plastics using super and subcritical media
US5908940A (en) * 1990-05-23 1999-06-01 Lipogenics, Inc. Processes for recovering tocotrienols, tocopherols and tocotrienol-like compounds
US5932101A (en) * 1996-08-29 1999-08-03 Eastman Chemical Company Process for fluid/dense gas extraction under enhanced solubility conditions
US5985344A (en) * 1997-09-02 1999-11-16 The Ricex Company Process for obtaining micronutrient enriched rice bran oil
US6187811B1 (en) 1998-10-28 2001-02-13 Lipogenics, Inc. Methods for treating benign prostatic hyperplasia using tocotrienols
US6569480B2 (en) 2001-04-30 2003-05-27 Donald R. Hall Liquefied gas extraction process
US20040030166A1 (en) * 2002-03-18 2004-02-12 Dick Copeland Methods for treating deodorizer distillate
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GB2152837A (en) 1985-08-14
DE3424614C2 (enrdf_load_stackoverflow) 1989-05-11
GB8416980D0 (en) 1984-08-08
GB2152837B (en) 1987-03-25
DE3424614A1 (de) 1985-01-17

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